Sulfur color and process of making same.



UNITED srarnsrarenr orrroniiiuwmt s. cumin, or rest, it. i

som me races of We can.

specifies not 0111mm fume.

. retentive-ear. 12,1968.-

. Aj litifi n as raters; zsi, nae. sea f6. aura;

= a dyestuif is produced.

I have this day signed an application (Serial No. 301,980) in which I disclose new sulfur colors made from non-crystallizable polysaccharids, aromatic chemicals, and sulfuring agents. I know of the invention by another, of new sulfur colors made from the sugars, aromatic chemicals and sulfuring agents. The non-crystallizable polysaccharids and the sugars form the group 0 chemicals known as the carbohydrates. (Tollens,

In making these substances the sulfuring agent em loyed consists substantially of a mixture of sixty parts by weight of sodium sulfid crystals and fifteen parts of sulfur, a ratio of four to one.

I have found that in practice sodium sulfid v v y and metaphenylme didminr-Into a suitable crucible weigh 40 crystals will, in boiling water, absorb about one third of their weight of ordinary sulfur.

In my newprocess- I increase the relative j so as to introduce intothe E c'. c. of water and boil five minutes. Then amount of sulfur, melt more sulfur than the sodium sulfid crystals will absorb. Thus with 240 parts water.

by weight of sodium sulfid crystals I may use 156 parts or even more, of sulfur, a ratio of 3 to 2 or more. I obtain thereby new colors, with properties superior to those above referred to. The same ingredients,

with the excess of sulfur, submitted to the same range of temperature yield colors of greatly increased tinctorial strength and either of greater brightness or of new tone impossible to obtain by the use of the smaller amount of sulfur. The excess sulfur reaction is also more facile and lends itself to a much broader and finer ran e and line of colors. Where with the smaller amount of sulfur a series of colors could be obtained plainlyseparable in shade from one another,

the differences are multiplied greatlyvwhere the excess of sulfur is used: the shades are brightened, or become more individualized.

An olive brownbecomes a cleaner cut olive,

Kohlenhydrate, Breslau, 1895, i -Vol. II, pp. 55-276).

a dark brown becomes a bloomy medium reddish brown of a greater specific commercial utility, while a medium cutch brown increases greatly in this brightness. In all cases the strengths of the colors are considerably increased, being doubled or even trebled in tinctorial power.

' That these stronger coloring matters are 1 new products and not simply a concentrated form of the colors obtained by using less ;sulfur, is shown by the resultant variations of shade, both in the dyeing and in solutions in solvents. For example, with metaph'enyl ene diamin and wheat starch the shade of the new color is much brighter, in fact brighter when usingl only 6 grams of metavphenylene dianiin, an can e obtained by using 12 grams of this exi'ensive chemical with the less amount (it sit fur. The difference between the results of the two methods is eyii more, arlted when used with wood f isawdust and me'taphenylene diamin, with i the excess sulfur a, medium yellow brown to olive brown bein obtained, while with the smaller amount 0 sulfur a dull cutch brown of a much redder tone is obtained.

The following examples may illustrate i the manner in which dyestuffs may be pro- 5 duced by my, newmethod.

Example 1. Wheat, cm 01': potato starch grams of sodium sulfid crystals and 26 grams of sulfur. Add 200 add 10 grams of wheat, corn or potato starch worked up intoa thinpaste in 50 c. e. of

Then add 6 grams of metaphenylene diamin. Boil slowl until the water has evaporated, Then raise the temperature adually in about half an hour to 300 C.

o'ntinue heating for another half hour, or until the full strength and shade of the color have been developed. Stir frequently so as to prevent burnin of the mass. The coloring matter thus 0 tained is readily soluble in cold water, in cold alkaline or cold sodium sulfid solutions,toa bright cutch brown solution, fairly soluble in cold alcohol to a yellowish brown shade, and dyes cotton directly in a salt bath a. fast bright cutch brown shade with the assistance. of sodium sulfid or salysoda. Ifdsired, the iiiicoiiciitratedfiilt. c'aii be dissolved in water and treated with an acid to secure the concentrated color prin- Y ciple. The dried precipitate obtained is inof the resultant colorin soluble in' cold water orcold alcohol, soluble in a solution of sodium sulfid c stals to a bri ht cutch brown solution, and yes cotton ectly in a salt bath, with the assistance of sal soda and sodium sulfid, fast bri ht cutch brown shades. The color may be developed by treating the dyed skein in a bath of peroxid of hydrogen, a bronzy yellow be' thus formed.

If in t e above formula 3 grams of blue stone are added as an ingredient, the shades matter are practically 'uninfluenced' there y, but its fastness to agents is enerally greatly im roved.

Example I. Gum arabz'ca nylene dz'amz'n.F orthe starch in Example I substitute gum arabic and use more water at the start. The resultant product is similar in characteristics to that obtained in Example I.

Ewample II I Wood sawdust and metaphenylene diamin.Into a suitable crucible weigh 40 grams of sodium sulfid crystals and 26 grams of sulfur. Boil up for five minutes. Then add 10 grams of wood sawdust and 6 grams of metaphenylene diamin.

. Boil one hour to impregnate the sawdust thoroughly w1th the sulfuring agents. Then cotton directly from a salt bath with the,

raise the temperature slowly to 320 C., covering the crucible to prevent burning of the contents. Heat at 320 C. for one 0111' or until the full strength and shade of the color have been developed. The coloring matter obtained is readily soluble in cold water, cold alkaline and cold sodium sulfid solutions to a rich medium yellowish brown solution, fairly soluble in alcohol, and dves assistance of sal soda or sodium sulfid fast medium yellow brown shades.

The colorin principle can be obtained in a purer and more concentrated form by precipitating with acids in the well-known manner. T e coloring matter thus obtained is insoluble in water and alcohol, soluble in a solution of sodium sulfid to a medilun yellow brown, and dyes cotton directly in a salt bath with the assistance of sal soda and sodium sulfid fast medium yellow brown shades. If the amount of metaphenylene diamin be increased to12 grams the coloring matter will be more olive in tone; but otherwise the properties and characteristics are similar.

E arample l V. Wheat starch and metadlnl trobenzene.For the metaphenylene diamin in Example Isubstitute metadinitrobenzene, gram for gram. The coloring matter obtained is a medium brown of an intermediate shade with characteristics generally similar to those of the colorin matter obtained from metaphenylene diamln. If in this example there be substituted for the 6 grams metaphetrobenzene grams of sulfid crystals or b heating 16 grams metadinitrobenzne wi th 40 grams of sodium sulfid crystals, coloring matters are formed which are considerably brighter intone.

Example V. Wheat starch and dinitrochlorbenzol-For metaphenylene diamin in Example I substitute dinitrochlorbenzol, gram for gram. The resultant product is similar in characteristics to that obtained from metaphenylene diamin, though darker in shade. It dyes cotton a rich 'cutch'brown of a yellowish tone. v

Example VI. Wheat starch and the sodiamsalt of sulfam'lic aside-For. metapheliylene diamin in Example I substitute the sodium salt of sulfanilic acid, gram for gram. The resultant coloring matter is similar in characteristics to that obtained by the use of metaphenylene diamin, but the It is a rich full shade is much darker. cutch brown of a reddish tone.

Colori matters may be obtained from other czii'hohydrates and aromatic chemicals. Thus a medium brown can be obtained from gum arabic and amidoazobenzol liydrochlorate; and browns from the condensation products of dinitrochlorbenzol with anilin, or with xylidin, and the starches, a' medium yellow brown and a cutch brown being obtained respectively. The sugars will yield coloring matters similar to those obtained from the starches by methods similar to that of Example I.

It will be noted that some of the abovementioned aromatic chemicals, such as metaphenylene diamin, are color-formers, that is 1. The process for the production of col-- oring matters consisting in heating a corbohydrate together with anaromatic chemical with sulfuring substances containing an excess of sulfur.

2. The process for the production of coloring matters consisting in heating a carbohydrate together with a color-forming aromatic chemical with sulfuring substances containing an excess of sulfur.

3. The process for the production of coloring matters consisting in heating a carbohydrate together with metaphenylene diamin with sulfuring substances containing an excess of sulfur.

fl. The process for the production of col oring matters consisting in heating a non comes crystallizable polysaccharid together with an aromatic chemical with sulfuring substances containing an excess of sulfur.

5. The process for the production of coloring matters consisting in heating a noncrystallizable polysaccharid together with a color-forming aromatic chemical with sulfuring substances containing an excess of sulfur.

6. The process for the production of coloring matters consisting in heating a noncrystallizable polysaccharid together with metaphenylene diamin with sulfuring substances containing an excess of sulfur.

7. The process for the production of coloring matters consisting in heating wheat starch together with an aromatic chemical with sulfuring substances containing an excess of sulfur.

8. The process forthe production of coloring matters consisting in heating wheat starch together with a color-formlng aromatic chemical with sulfuring substances containing an excess of sulfur.

9. The process for the production of coloring matters consisting in heating wheat starch together with metaphenylene 'diami n with sulfuring substances containing an excess of sulfur. I

10. The process for the roduction of coloring matters consisting in heating wheat starch together with metaphenylene diamin with sodium sulfid and sulfur in excess of the quantity which the sodium sulfid can absorb.

11. As a new article of manufacture, the coloring matter which can be produced by heating wheat starch together with metaphenylene diamin with sodium sulfid and sulfur in excess of the quantity which the sodium sulfid can absorb, which is readily soluble in cold water, in cold alkaline or cold sodium sulfid solutions to a bright cutch brown solution, fairly soluble in cold alcohol to a yellowish brown shade, and which dyes cotton directly in a salt bath a fast bright cutch brown shade with the assistance of sodium sulfid or sal soda, and which when precipitated by acids forms a coloring matter water or cold alcohol, soluble in a solution of sodium sulfid crystals to a bright cutch brown solution, and dyes cotton directly in a salt bath, with the assistance of sal soda and sodium sulfid, fast brown shades.

In testimony whereof, I have hereunto signed my name in the presence of two subscribing witnesses.

. EDWARD S. CHAPTN.

Witnesses:

FRITZ v. BRIESEN,

JOHN A. KEHLENBECK.

which is insoluble in cold 

